Chlorinated 4,5,6,7,10,10-hexachloro-4,7-endomethylene - 4,7,8,9 - tetrahydrophthalane insecticides



United States with This invention relates to and has as its objectthe.production of novel-chlorinated 4.5 6.7.1Q.10-hexachloro-4.7-endomethylene-4.7.8.9-tetrahydrophthalane, which have been found toconstitute extremely eifective --insecticides.

The 4.5.6.7.10.10 hexachloro 4.7-endomethylene-4.7.8.9-tetrahydrophthalane has the formula:

The insecticides, in accordance with the invention, which are obtainedby chlorinating the above product, may contain 6.5 to 1'0 chlorine atomsper molecule and preferably contains 8 chlorine atoms ;per molecule, i.e.,it is 1.3.45.6.7 J10.1tl octachloro t.7-en'domethylene-4i7k8.9-tetrahydrophtha lane. These insecticides, due to their expectionallyhigh activity and wide effective range, are extremely valuable forcombattingundesirable insect life. The novel chlorination products inaccordance with the invention, are practically insoluble in water, areextremely stable and resistant in air toward moisture, and toward acidand alkaline materials, and may be used alone or in any desiredconventional admixture as an insecticide. For example, the novelchlorination produ'cts may be admixed with other insecticides and/ornon-ins'ecticidally active diluents.

The 4.5.6.7.10.10 hexachlor'o 4.7-endomethylene-4.7.8.9tetrahydrophthalane used as the starting material for theinsecticides according to the invention can be produced byvariousmethods.

Hexachloroeyclopentadiene can be converted with cis- '2-bu'tene-L4-diolin the presence of solvents at elevated temperature into 1.45.6.7.7heXachloro-23-dimcthyldlbic.yclo-'(2. 2.l) 5-heptene according to thefollowing equation By dehydration this addition ,product undergoescyclization to form 4.5.6.7.10.'1'0 hexachloro-4I7-endomethy1-one-4.7.8.9-tetrahydrophthalane according to the following equation:

ent

Patented Sept. :19, 1961 Both of the conversions may also be effectedsimultaneously, but with a poorer yield, by heatinghexachlorocyclo-pentadiene and cis-2-butene-L4-diol in the heterogeneousphase in .the absence or a solvent.

The conversion of hexachlorocyclopentadiene with ois- 2-butene-L4-diolis best effected in solvents in which the two starting components aresoluble in order that the reaction may proceed in the homogeneous:phase. Examples of particularly well suited solvents are'dioxane,tetrahydrofurane, and alcohols having more than two carbon atoms. Thequantitative proportion of hexachlorocyclopentadiene tocis-2--butene-1.4-diol maybe selected within wide limits. However, -astoichiornetrical quantitative proportion should generally be used. Thequantity of the solvent is dependent upon the quantity required toconvert both of the non-miscible reactants, at the reaction temperatureused, into a homogeneous phase. .The reaction temperature mayrangebetween and 150C.

The reaction time is determined by the temperature and the quantity 'ofthe solvent. The higher the reaction temperature and the "smaller 'thequantity "of solvent, :the more rapidly the conversion proceeds. At *atem-' perature of C. and with the use of dioxane as the solvent, thereaction time, with an optimum conversion, amounts to 2-3 days. Whenusing solvents boiling below the -reaction temperature, the conversionhasto be efiected :in pressure vessels. The separation "of the 1.4.5.6.7.7-hexachloro 2.3 dimethylol -'bicyclo(2.2. 1;)-- "5-heptene iseffected by distilling on the solvent and the unconverted startingproducts under a reduced pressure; In this distillation, the additionproduct is obtained as the residue consisting of 'a colorless to faintlydark colored crystal mass. It may, either immediately or after tocrystallization, be subjected to subsequent dehydration. Chloroform isparticularly suitable as solvent forther'eaction product.

The dehydration is expediently effected in an'o'r'ganic solvent by meansof catalytic quantities of strong nonvolatile acids. Suitabledehydrating agents are sulfuric acid, phosphoric acid, pyrophosphoricacid, toluene 'sultonic acid, and others. The quantity of thedehydrating agent may range between 0.1 to 5% by weight of the quantitycharged of the "addition product. The solvents used may be suchnon-reactive organic compounds which azeotropically'remove the waterformed from the reaction product. Particularly well suited are tolueneand hem zene. The quantity of the solvent is to be chosen such as tojust dissolve the 1.4.5.6.7;7 hexachloro-2L3-"dimethlolbicyclo(2.2.l)-5-heptene to be dehydrated when boiling. The dehydrationis 'expe'diently accomplished in an apparatus in which the waterazeotropically removed may bewithdrawn from the reaction space and the"solvent, after separation of the water, may be returned to the reactionspace.

The processing of the reaction product is effected by concentrating thereaction solution and crystallizin'g "the 4.5.6.7.l0.l0 hexachloro-AJendomethylene-4l7.8i9- 'tetrahydrophthalane.

The direct conversion "of'the hexachlorocyclopentadiene withcis-2-butene-l.4-diol without the use of a solventm'ust be effected withvigorous stirring of the heterogeneous reaction mixture at temperaturesof 100-120 C. "Thereby, the pure phthalane product 'slo'wly crystallizesfrom the reaction mixture in a coarse crystalline form. The reactionproceeds substantially slower than in the homogeneous phase and'requiresa reaction time of 3 to 5 days with the yield bein'g 2030% of thetheoretically poss'ilile quantity. I

The 4.5.'6.7.'10.1O heXachloro 4.7 endomethylene-='4'.7.'8l9-tetrahydrophthalane used as the starting material accordance'with the invention can also be produced type synthesis proceedingaccording to the following equation:

The conversion is accomplished by heating dihydrofurane withhexachlorocyclopentadiene alone or in the presence of a diluent. Thediluents used must be nonreactive with the hexachlorocyclopentadiene anddihydrofurane. Examples of suitable diluents are benzene, toluene,dioxane, and saturated ethers.

- The mol ratio of hexachlorocyclopentadiene to dihydroiurane isexpediently chosen such as to have an excess .of one of the reactants,preferably of dihydrofurane. The reaction may be effected by extendedheating of the components with reflux of the excess dihydrofurane or attemperatures of 80-120 C. in a pressure tube. When operating in thepresence of a diluent, equimolar quantities of the starting materialsare to be used. In this case, the reaction is effected in a pressuretube at 90450 C. The reaction time is 2 to 30 hours depending upon thereaction temperature used. The reaction may also be effectedcontinuously by slowly passing a mixture of the two reactants togetherwith a high boiling hydrocarbon as a diluting agent through, forexample, heated tubes. When cooling the reaction solution, the additionproduct separates in a crystalline form.

uct is easily removed by recrystallization from methanol .0r 'pet'roleumether. A further purification is possible by sublimation under vacuum.

Instead of using pure hexachlorocyclopentadiene, the conversion with2.5-dihydrofurane may be effected with the use of mixtures which, inaddition to hexachlorocyclopentadiene, contain other materials,especially partially chlorinated cyclopentadienes.

When preparing hexachlorocyclopentadiene by the method reported by E.Straus and co-operators (see Berichte der Deutschen ChemischenGesellschaft, vol. 63, page 1884 (1930)) by the action of sodiumhypochlorite solutions on cyclopentadiene, there are formed, in additionto hexachlorocyclopentadiene, chlorinated cyclopentadienes having lessthan 6 chlorine atoms in the molecule. The separation of the purehexachlorocyclopentadiene by fractional distillation of the crudeproduct causes considerable difiiculties and entails great losses ofhexachlorocyclopentadiene.

While, as stated by Straus, the conversion of cyclopentadiene withsodium hypochlorite solution results in a reaction product the yield ofwhich, based on weight, corresponds to 82% of the theoretical quantitycalculated on hexachlorocy'clopentadiene, only 53.6% of purehexachlorocyclopentadiene can be separated from this reaction product.This corresponds to a yield of only 44% of the theoretically possiblequantity based on the cyclopentadiene charged. The remaining 46.4% ofthe reaction product could hitherto not be utilized for furtherconversions.

This modified working method allows the direct conversion of thehexachlorocyclopentadiene contained in the crude products with2.5-dihydrofurane with the elimination of the uneconomical processing bydistillation which involves much loss. It has very surprisingly beenfound that the hexachlorocyclopentadiene contained in the crude productreacts more rapidly with 2.5-dihydrofurane according to the Diels-Alderto form4.5.6.7.l0.10-hexachloro-4.7-methylene-4.7.8.9-tetnahydrophthalane thanthe 4 low-chlorinated cyclopentadienes which are converted intochlorinated dicyclopentadienes. Thereby, a much better utilization ofthe hexachlorocyclopentadiene contained in the crude product is achievedthan is possible by the separation of this compound by distillation.

The major part of the reaction product obtained by the conversion of thecrude product with 2.5 -di.hydrofurane consists of 4.5.6.7.10.10hexachloro 4.7 methylene- 4.7.8.9-tetrahydropthalane. As side-productsit contains a small amount of reaction products of dihydrofurane withthe low-chlorinated cyclopentadienes and of reaction products of thelow-chlorinated cyclopentadienes with each other.

For the conversion mentioned above there are suitable all reactionproducts which form by the action of alkali hypochlorite solutions oncyclopentadiene, i.e., the untreated reaction product as well asproducts which form by distillation of this crude product. The2.5-dihydrofurane should be free from other unsaturated compounds,especially from 2.3-dihydrofurane. The conversion is effected by heatingthe chlorinated cyclopentadiene mixtures with 2.5-dihydrofurane per seor in the presence of a diluent. The diluents used must be non-reactivewith hexachlorocyclopentadiene and dihydrofurane. Examples of suitablesolvents are benzene, toluene, dioxane, and saturated ethers. The molratio of the starting products is expediently chosen so that an excessof dihydrofurane is present.

If the reaction is carried out in the absence of diluents, a molar ratioof 1 part of hexachlorocyclopentadiene mixture to l.5-3 parts of2.5-dihydrofurane is of particular advantage. The reaction may beaccomplished by extended heating of the components with refluxing of theexcess dihydrofurane or at temperatures of -150 C. in apressure-resistant tube. In the presence of a diluent, equimolar amountsof the starting materials may be processed. The reaction time is 2-30hours depending upon the reaction temperature used.

The processing of the reaction products is eifected by distilling oifthe unconverted reactants and the diluent which may be present. Thereaction products obtained in this manner are solid or semi-solid masseswhich are generally of dark color and which contain about 60-80% of4.5.6.7.10.10-hexachloro-4.7-methylene-4.7.8.9-tetrahydrophthalane andcan easily be purified by recrystallization. This purification, however,is not absolutely necessary, it being possible to chlorinate theunpurified reaction products.

The chlorination of the 4.5.6.7.10.l0 hexachloro-4.7- endornethylene4.7.8.9. tetrahydrophthalene which, according to the invention, is usedas the starting material may be effected by means of processes whicheitect a substitution in the tetrahydrofurane ring of the 4.5.6.7.10. 1Ohexachloro 4.7-endomethylene-4.7.8.9-tetrahydrophthalane. This resultsin a chlorination product which, when having taken up two additionalchlorine atoms, has an optimum of insecticidal properties.

The insecticides of the invention may be obtained by introducing gaseouschlorine into the solution of the 4.5.6. 7.10.10 hexachloro4.7-endomethylene-4.7.8.9-tetrahydrophthalane in carbon tetrachloride orother chlorohydrocarbons suited for chlorinations in the liquid phase orother inert solvents. However, it is also possible to use solventswhich, by taking up chlorine, are converted into chlorohydrocarbons,especially benzene, toluene, and others. Moreover, compounds from whichthe chlorine can easily be split ofi are also suitable chlorinationagents.

The reaction may also be efiected without the use of a solvent. In thiscase, the hexachlorophthalane is directly contacted with chlorine or thechlorinating agent. Room temperatures are generally sufficient for theconversion. It is of advantage, however, if the chlorination whichproceeds as a chain reaction is stimulated and kept going by heat,light, or radical-forming substances. The chlorination may be effectedin glass vessels or enamelled scanner metal vessels in batchwise orcontinuous operation. Depending upon the working conditions and whetheror not a solvent is used the absorption of chlorine is observedgravimetrically or by continuous sampling from the reaction vessel anddetermination of chlorine. Thereaction can be considered as beingterminated when the degree of chlorination desired is reached. This isin general a total of 8 gram atoms of Cl per mol of starting material,but products of 6.5 to gram atoms of Cl per mol are also usable andeffective.

When using a solvent, the separation of the active substance is effectedby distillation or crystallization. This results in a white crystallinesubstance which can be processed into pesticide formulations withoutfurther purification. When maintaining a degree of chlorination of 8gram atoms of chlorine per mol of starting material, maximum activity isreached on Musca domestica, In this case the chlorination product is alargely uniform substance which may be recrystallized from n-heptane andhas then a melting point of ll22 C. (corrected). This substance isobviously the endo-1.3.4.5.6.7.l0.10- octachloro4.7-endomethylene-4.7.8.9-tetrahydrophthalane. In addition to thiscompound, however, especially if chlorination products having less ormore than 8 gram atoms of chlorine in the molecule are involved, otherchlorinated compounds .are doubtless present in the reaction product.

The chlorination mixtures or also the pure endol,3.4. 5.6.7.1010octachloro-4.7-endomethylene-4.7.8.9-tetrahydrophthalane obtained bymeans of the process of the invention can easily be used for thepreparation of commercial formulations. Emulsions, suspensions, dustingand strewiug agents, wettable dusts, sprays, fumigatiug agents oraerosols may, be produced from them. For the emulsions there may beused. emulsifiers such as higher molecular weight ethylene oxidecondensation products, alkyl aryl sul-fonates, fat alcohol sulfonates,etc. Suitable solvents arealcohols, ketones, aromatic, aliphatic andcyclic hydrocarbons, animal and vegetable oils and similar materials.Suitable carrier materials for the preparation of spray powders anddusts are talcum, kieselguhr, kaolin, bentonite or other pulverulentmaterials. In the further processing of the wettable dusts the additionof wetting agents, protective colloids and adhesives is required.Substances of this kind, however, may also be added to other types offormulations. For the preparation of aerosols the use of propellants andsolvents such as halogenated methanes is required. The active materialmay also be processed to insecticide formulations in mixture with otherinsecticide toxicants which undergo no chemical reaction with the activematerial.

The following examples are given by way of illustration and notlimitation:

EXAMPLE 1 A mixture of 80 gms. of hexachlorocyclopentadiene, gms. ofcis-2-butane-l.4-diol, and 75 cc. of dioxane was heated at 120 C. forthree days in a thick-Walled glass tube. After evaporation of thedioxane at 100 C. under a 20 mm. mercury vacuum the unconvertedhexachlorocyclopentadiene and cis-2-butene-L4-diol were distilled oilunder a 0.3 mm. mercury vacuum and a bath temperature of 130 C, Theremaining distillation residue was dissolved hot in chloroform, thesolution was decolorized with active carbon and, after filtration,cooled to -20 C. in a refrigerator. Thereby, 60 grams of 1.4.5.677hexachlor-Z.S-dimethylol-bicyclo (2.2.l)-5- heptene crystallized ascolorless flakes which had a melting point of 199 C. Evaporation of themotor liquor resulted in additional 16.5 gins. of the Diels-Alder adductso that the total amount was 76.5 gms. corresponding to a yield of 75%of the theoretically possible quantity based on thecis-2-butene-1.4-diol charged.

Analysis: C H O CI Molecular weight: 360.89.

Calculated, percent Foun Percen' Seventy-five grams of the1.4.5.6.7.7-hexachlor-2.3 dimethylol-bicyclo(2.2.l)-5heptene producedwere heated with a solution of 350 cc. of toluene, 2 cc. of concentratedsulfuric acid, and 5 cc. of water in a dehydration apparatus withvigorous reflux. The apparatus consisted of a reaction flask in whichthe toluene solution of the prodnot to be dehydrated was contained, andwas equipped With a glass column with a reflux condenser mountedthereupon and a laterally attached water separator. The rising toluenevapors which azeotropically entrained the dehydration water werecondensed in the cooler, dropped into the separator where a separationinto a lower aqueous phase (dehydration water) and an upper toluenephase, took place. The top toluene phase passed continuously back intothe reaction flask. After three hours, 9 cc.

of water had separated in theseparator. The hot toluene FoundCalculated,

percent percent EXAMPLE 2 A mixture of 80 gms. ofhexachlorocyclopentadiene, 25 gms. of cis-2-butene-l.4-diol, and cc. ofdioxane was heated for three days while being refluxed. The reactionsolution was then processed in the .rnanner described in Example 1. Thedistillation residue was a colorless crystalline material and wasdissolved in 250 cc. of toluene. The solution was mixed with 3 cc. ofdilute sulfuric acid and dehydrated in the apparatus described inExample 1. After two hours, the reaction was completed. The reactionmixture was processed in the manner described in Example 1. Thisresulted in 40 grams of 4.5.6.7.10.l0-hexachlor-4.7-endomethylene4.7.8.9-tetrahydrophtha1ane.

EXAMPLE 3 A mixture of grams of hexachlorocyclopentadiene, 25 grams ofcis-2-butene-1.4-diol, and 75 cc. of dioxane was heated at 140 C. for 24hours in the manner described in Example 1 and the reaction product wasprocessed in the manner described in Example 1. After having distilledoff all materials volatile at .C. and a 0.3 mm. mercury pressure thereremained 80 grams of crude l .45.6.7.7-hexachlor-2.3-dimethylol-bicyclo-(2 .2. l 5-heptene as a darkcolored crystalline material. This crude product was heated for fourhours with 400 cc. toluene and 5 cc. of 50 wt. percent sulfuric acid inthe dehydration apparatus described in Example 1 with vigorous reflux.Decolorization of the hot toluene solution with active carbon,concentration of the filtered solution, and cooling to 20 C. resulted in68 grams of 4.5 .6.7 10. 10-hexachlor-4.7 -endomethylene-4.7.8.9-tetrahydr'ophthalane.

EXAMPLE 4 and 44 grams of cis-2-butene-L4-diol was heated for three dayswith stirring in a two-necked flask with stirrer and reflux condenser ona water bath. During this time, 40 grams of4.5.6.7.10.lO-hexachlor-4.7-endomethylene- 4.7.'8.9-tetrahydrophthalanein a crystalline form had separated. After having drawn off the reactionsolution andwashed it with cold alcohol, this product could be obtainedin a pure form having a meltingpoint'of 230 C.

v EXAMPLE 5 1 A mixture of 27.3 grams of hexachlorocyclopentadiene andlOgrams of dihydrofurane was heated at 100 C. for hours in apressure-resistant vessel. The reaction product was mixed with 100 cc.of petroleum ether and cooled to C. in a refrigerator. After havingdrawn on the precipitated crystal slurry, grams of crude4.5.6.7.10.l0-hexachlor-4.7-endomethylene-4.7.8.9- t'etraliydrophthalanewere obtained which, by recrystallization from methanol, was recoveredas colorless crystals having am'elting point of 232C. I

- Analysis: C H OCI Molecular weight: 342.88.

Calculated, 7 Found, percent percent EXAMPLE 6 grams ofhexachlorocyclopentadiene, 7 grams of dihydrofurane, and 50 cc. ofbenzene was heated'at 120"C. for 16 hours in a pressure-resistantvessel.Thereaction mixture-was freedfrom benzene by evaporation under vacuum ona water bath and'diss On cooling, .25 grams EXAMPLE 7 A mixture of 27.3grams of hexachlorocyclopentadiene andZO grams of dihydrofurane washeated for 24 hours on a water bath. Then the excess dihydrofurane wasdistilled off and the residue was mixed with 50 cc. of petroleum ether.fter having drawn oil the mixture cooled to l0 C. the yellowish crystalslurry obtained was washed with much methanol. Thereby; 20 grams of4.5.6.7.10.l0-hexachlor-4.7-endomethylene-4.7.8.Q-tetrahydrophthalanewere obtained in the form of colorless crystals.

EXAMPLE 8 100 grams of4.5.6.7.10.10-hexachlor-4.7-endomethylone-4.7.8.9-tetrahydrophthalanewere dissolved in'300 cc. of carbon tetrachloride by heating. Chlorineat a rate of 25 liters/hr. was introduced into the solution at about 70C. while irradiating with ultraviolet light. During the chlorination thesolution was vigorously stirred. After ten minutes the reaction wasterminated and'the solution was evaporated under vacuum. The residueconsisted of 110 grams of a white crystallinc'substance which had thecomposition C H OCI as determined by elementary analysis. I

g Y EXAMPLE 9 100 grams of4.5.6.7.l0.10-hexachlor-4.7-endornethylone-4.7.8.9-tetrahydrophthalenewere dissolved in 300 cc; of carbon tetrachloride in the mannerdescribed in Example 8 and chlorinated at 70 C. for- 40 mi nute with 25liters/hr. *ofchlbrine.".x'lhe crystalline product (120 grams) remainingafter the chlorination and evaporation of the solvent had the empiricalformula CgH Ocl When recrystallized from n-heptane, there remained asubstance which had a melting point of 122 C. Analysis: C H OClMolecular weight: 411.78. 7

Calculated, Found,

percent percent EXAMPLE 10 5 100 grams of4.5.6.7.10.10-hexachlor-4.7-endomethyl ene-4.7.8.9-tetrahydrophthalanewere dissolved in 300 cc. of carbon tetrachloride in the manner setforth in Ex" ample 8 and treated for two hours with 25 liters/hr. ofchlorine. After evaporation there remained grams of a crystallineproduct having the empirical formula CgHgOClgi EXAMPLE 11 EXAMPLE 12 I(c) 9 liters of a 2.09-norma1 sodium hypochlorite solu tion which stillcontained 0.2 mol of free sodium hy droxide was placed into a reagentbottle having a capacity of 10 liters and being capable of being cooledwith flow-I ing water. This solution, while vigorously stirring, was atonce mixed with 110 gms. of freshly distilled cyclo-' pentadiene. Thestirring with a high-speed stirrer was continued for 15 minutes. Duringthis time, the tem-- perature increased to 40 C. After 30 minutes aheavy yellow, viscous liquid separated from thesolution and waswithdrawn. i

The remaining reaction solution was again cooled to 15 C. and mixed with110 grams of freshly distilled cyclopentadiene while stirring. Thestirring was con: tinued for 15 minutes. In this time an additionalquantityofthe heavy yellow reaction product formed. After 1 hour it wasseparated and combined with the first prod not. ..In this manner, atotal of 728 grams of raw re-l. act-ionproduct of a pungent smell andyellow-brown color was obtained fromthe total of 220 grams ofcyclopentadiene charged. This reaction product was designated as ProductR. Its refractive index was n =1.5611. It contained 25.79% of carbon,0.68% of hydrogen and 73.36% of chlorine. 1

(11) 175 grams out of 200. grams of the product R obtained inthis mannerwere distilled off at 20 mm. Hg in a simple distilling apparatus andthis fraction was used as Product 5 for the conversion with 2.5-dihydro:furane. The refiractive index of this mixture was, n =l.5S85.

(c) grams out of 200 grams of the Product R were distilled off in themanner described under (b) above andthe fraction obtained was used asProduct T for the further conversion. This mixture had a refractiveindex of n =1.5578.

EXA MPLE 13 9. was transferred into a three-necked flask equipped with astirrer, a reflux condenser and a thermometer. While stirring andirradiating with a 500 watt mercury vapor lamp, a stream of chlorine of21 liters/ hr. was introduced into the solution which was heated to70-80 C. After 30 minutes, the solvent was distilled off at a mm.mercury pressure on a Water bath. This resulted in 76.5 grams of asemi-solid Product In the analysis of which showed the followingcomposition:

(c) 54.6 grams of the Product R from Example 12(a) were reacted with21.0 grams of 2.5-dihydrofurane and processed in the same manner asdescribed in Example 13(a). The subsequent chlorination was effected for3 hours at the same flow rate of chlorine. After evaporation of thecarbon tetrachloride there remained 87.2 grams of a semi-solid ProductIc which had the following composition:

EXAMPLE 14 (a) A mixture of 54.6 gins. of the =Product S described inExample 12(b) and 21 grams of 2.5.-dihydrofuranc were heated at 120 C.for 20 hours in a closed tube. Following this, the unconverted2.5-dihydrofurane was distilled off under a 20 mm. mercury pressure fromthe reaction mixture obtained. The residue thereby obtained, in a carbontetrachloride solution, was chlorinated for minutes in the mannerdescribed in Example 13(a) using a flow rate of 21 liters/hr. ofchlorine. The Prod- 1101: Ha obtained when evaporating the carbontetrachloride comprised 78.5 grams and had the following composition:

C=30.58% H= 1.75% O=3.79% O1=64.30%

(b) 54.6 grams of the Product S were reacted with 21 grams of2.5-dihydrofurane in the manner described in Example 13(a) and thereaction product obtained was subsequently chlorinated for 45 minutes atthe same flow rate of chlorine. After evaporation of the carbontetrachloride there remained 83 grams of a semi-solid Product IIb whichhad the following composition:

O=3.56% Cl=66.02%

(c) 54.6 grams of the Product B were reacted with 21 grams of2.5-dihydrofurane in the manner described Example 14(a) and the productobtained was chlo- 10 rinated for 3 hours. The Product He obtained afterevaporation of the solvent comprised 91.3 grams and had the followingcomposition:

C=26.35% H=1.2l% O=3.27% Cl=69.12%

EXAMPLE 15 (a) 54.6 grams of the Product T described in Example 12(n)was reacted with 21 grams of 2.5-dihydrofuranein the manner described inthe Examples 12 through 14. Following this, the reaction productseparated was chlorinated for 60 minutes. After evaporation of thesolvent there remained 83.8 grams of a Product Illa which had thefollowing composition:

C=28.53% H=1.56% -O=3.68% Cl=61.88%

(b) 54.6 grams of the Product T were reacted with 21 grams of2.5-dihydrofurane in the manner described in Example 15(a) and thereaction product thereby obtained was chlorinated for 3 hours in themanner pre viously described. The Chlorination Product IIIb ob.- tainedafter evaporation of the carbon tetrachloride comprised 88 grams and hadthe following composition:

The activity of the new insecticides was determined by means of amodified method described by W. M. Hoskins and P. S. Messenger(Agricultural Control Chemicals, Advances in Chemistry Series 1, 93-98(1950)) by establishing the lethal dosage for 50% and respectively, of abreed (LD values and 1D,, values, respectively) with Musca domestica.The test was carried out with the use of 4 days old females. Ascomparison, the LD and LD values of the pure active substance of someknown insecticides are listed.

Table 1 Relative toxicity after 24 hours to 4 days old females ofSubstance Marco domestz'ca 50% 90% mortality mortality 74..3.4.5.6-hexachlorocyclohexane 10 10 p,p-dichlordiphenyl-triehlorethane0. 63 3. 1 1. 2.3. 4. 12. 12 -hexachlor l. 4. 5. 8 dimethylene1.4.5.8.910-hexahydronaphthalene (Aldrine)..- 10 101.2.3.4.12.12-hexachlor -6.7 epoxy 1.4.5.8dimethylene-l.4.515.7.8.9.lo-octahydronaphthnlene (Dieldrine) 3. 6 1OChlordane 1.5 0. 2 0,0 diethyl thiophosphoric acid O p nitrophenylester70% (E 605 forte) 800 x.y.4.5.6.7.10.10-octachlor 4.7 methylene1.2.4.7.-8.9-hexahydroindene 10 10 Chlorination product of Example 8 43 200Chlorination product of Example 9-. 300 67,0 Chlorination product ofExample 10. 10 25 Chlorination product of Example 11 60 80 It isinteresting to note that the active substance ac cording to theinvention has a markedly good initial efiect as may be seen from thefollowing table in which the hours are listed.

Table 11 Relative toxicity after 2 hours to 4 Substance days old femalesof Musca domestica- 50% upside down position-1.2.3.4.5.6.-hexaehlorooyclohexane 1op,p-dichlrdiphenyl-trichlorethane 1. 25 1.2.3.4.1212 hexachlor 1.4.5.8dimethyl 8.9.10-hexahydronaphthalene (Aldrine) 0. 36

0.72 0. 04 0,0 diethyl thio hosphoric acid O p nitrophenylester 70% E605 forte) x.y.4.5.6.7.l0.10 octachlor 4.7 methylene 4.2.4.

7.8.9-hexahydroindene 0. 21 Chlorination product of Example 8 a 3. 1Chlorination product of Example 9- 20. 8 Chlorination product of Example10 1. 0 Chlorination product of Example 11 6. 3

It is already known that Diels-Alder addition compounds fromhexachlorocyclopentadiene and unsaturated compounds, as such or afterfurther chemical conversion, exhibit insecticidal properties and aresuitable for combating noxious insects. The insecticides known under thetrade names Chlordane and Heptachlor, for example, are chlorinationproducts of the addition compound from hexachlorocyclopentadiene andcyclopentadiene. The in secticide known under the trade name of Aldrineis an addition compound from hexachlorocyclopentadiene andbicycloheptadiene while Dieldrine" is the tradename ofthe epoxy compoundof Aldrine. Besides these generally known insecticides there are stillother compounds derived from hexachlorocyclopentadiene in the manner setforth, which possess insecticidal properties which, however, are not aspronounced as those of the compounds previously mentioned. 1 r

The particular advantage of the use, in accordance with the invention,ofl.3.4.5.6.7.l0.10-octachlor-4.7-endomethylene-4.7.8.9-tetrahydrophthalaneas an insecticide resides in the surprisingly high insecticidal activitywhich is by many times better than that of all compounds of this typehitherto known. The activity of the new compound is also substantiallyhigher than that of the known insecticides made up ofchlorine-containing hydrocarbons such as -y-hexachlorocyclohexane(Lindane) or p-dichlordiphenyl-trichlorethane (DDT). In some cases thenew compounds are even of somewhat higher activity than knownphosphorous insecticides such as p-nitrophenyl-diethyl-thiophosphate (E605, Parathion). .By itsextremely high insecticidal activity,l.3.4.5.6.7.l0.l0-octachlor-4.7-endomethylene-4.7.8.9-tetrahydrophthalane fundamentally differs from theknown chlorine-containing hydrocarbon insecticides. To reach a giveneffect, the quantities required of the compound of the invention aresubstantially. lower than those required of the known chlorinecontaininginsecticides so that it is possible to work with extremely lowconcentrations.

The same high activity of the compound of the invention was also foundon noxious insects other than Musca domestica by means of laboratorytests and field tests. Tests have been carried out on a number ofinsects from the group of the sucking insects, which are difiicult tocombat and the test results have been listed in Table III. Thecomparative agent used was in all cases E 605 (1) which had a content of47.7% of pure active material I(p-nitrophenyl-diethyl-thiophosphate).When applied in a concentration of 0.035% and a quantity of 600 liters/hektar (=243 liters/acre) there results a dosis applied oflOOgrams/hektar (4O grams/acre) of pure active materia V H 4 Thecompound of the invention, in contrast to this, was-used in a quantitywhich corresponded to a dosis applied of only 24 grams of pureactive'material per acre (60 gms./hektar). c

"Table III suomo msno'rs A: Compound of the invention (24 gmsJacre) B: E605 (I) (40 grams/acre) L: Laboratory tests F: Field tests Per- Percentcent kill Per- Insecof infor cent Time Type Insect Pest ticides sectsinkill in of fallen sects at the days Test to fallen plant ground toground A 5 100 100 1 L Doralis pomi 1 A 100 100 1 L B 76 100 100 1 LDoralis Youn n mals. g8 g3 i E Pomaphis g g Ddmlisfcbae i i Wooly appleaphid {A 100 2 F. (Eriasomu Zrm'igerum). B 100 2 F 1 Germandesignationsof Doralis pomi--Griin1e Apfelblattlaus, Pomaphis=mehligePfleumenlaus, Domlis fubae=schwarze Bohenblattlaus.

The wide efiective range of the compound of the invention may be seenfrom Table In this case, the eflect of the new agent on the potato bugwas investigated as an example of biting insects. The comparativepreparation used was a mixture of Lindane and DDT which is known underthe trade name of Aktiv-Gesapon (Neu)" (Active Gesapone New).

Table IV A= Compound oi the invention (dilution 1:10,000) i B=Mixture ofLindane and DDT (tradename Aktiv-Gesapon Neu) (dilution 1:3,00U4,000)Figures without parentheses: percent kill Parentheses figures: percentof insects severely damaged.

Y Kind of Insect Pest Agent. 1st day 3rd day 6th day t 1481201:-

I ory es g z jg gg gfljgi A 5 so (40) so (10)]Applied am) young bugs B o(as) 10 (so) 55 (45) I. to-iood. Do A 6 E95) 40 E60) (O) }Applled: B 0so) a 95) to ugs; Potato bugs L4 {A 0 (95) 65 (35) 95 (5) }Appliod' i 22$323 $2 $323 332i .t i i pp 16 bugs L3 {B o 100) 55 (45) 70 (so) tobugs.

The insecticidal activity of the chlorination products preparedaccording to Examples 13 through 15 may be seen from the following TableV. This table indicates: that, the insecticidal activityof thechlorination products of the invention increases as the chlorine'conteiit ini creases until a maximum is reached, and decreases withhigher chlorine contents reach maximum activity the insecticidalactivity of the reaction products is constantly observed duringthe'chlorination by sampling in order to allow timely discontinuation ofthe reaction.

Table V Toxicity I Chlorine Relative after Chlorination products ac-Chlorine atoms after24 2hours cording to Examples 13-15 content, perhours t "60% v percent molecule, ,LDr up ar; 1' '.down.:.

position -y-hexachloro-cyclohaxane 40 40 Ia 62.61 6.1 80 5 66.43 7.2 30050 67.83 7.6 170 25 64.33 6.6 48 9 66.02 7 400 25 69.12 8.]; 25 sass 7v12o 67.77 a 7.6 240 a s While the initial toxicity of the chlorinationproducts of the invention ranges only little below that of'y-hexachlorocyclohexane, their long lasting activity is by ten timeshigher than that of 'y-hexachloro-cyclohexaue.

The products of the invention may also be used in mixture with otherinsecticides, such as with 'y-hexachlorocyclohexane, 1.2.3.4.l2.l2hexachlor 1.4.5.8 dimethylene-l.4.5.8.9.l-hexahydronaphthalene,1.2.3.4.12. 12-hexachlor-6.7-epoxy-l .4. 5 8-dimethylene 1.4.5 .6.7 .8.9. lO-octahydronaphthalene.

We claim:

1. As a new chemical compound, a chlorinated product of4.5.6.7.l0.l0-hexachloro-4.7-endomethylene-4.7.8. 9-tetrahydrophthalanecontaining an average of 6.5 to 1'0 chlorine atoms per molecule.

2. As a new chemical compound,1.3.4.5.6.7.10.10-octachloro-4.7-endomethylene-4.7.8.9-tetrahydrophthalane.

3. Procms for the production of4.5.6.7.10.10-hexachloro-4.7-endomethy-lene 4.7.8.9 tetrahydrophthalane,which comprises heating a mixture of cis-2butenel.4- diol andhexachlorocyclopeutadiene at a temperature between about 100 and 150 C.,thereafter separating the water from the reaction product formed in anazeotropic distillation with toluene and small amounts of sulfuric aciddehydrating the l.4.5.6.7.7-hexachloro-2.B-dimethylbicyclo(2.2.1)-5-heptene formed by said heating, and recovering from thereaction mixture the 4.5.6.7.10.l0- hexachloro-4.7-endomethylene-4.7.8.9tetrahydrophthah ane formed.

4. Process according to claim 3, in which said heating is efiected withreactants dissolved in an inert solvent.

5. Process according to claim 3, in which said heating is efiected at atemperature between about 100 and 120 C. with a heterogeneous mixture ofthe reactants and in which said separation of water is substantiallysimultaneously eflected at said temperature.

6. Process according to claim 3, in which the 4.5.6.7.10.10-hexachloro-4.7-endomethylene-4.7.8.9 tetrahydro- '1'4 phthalaneformed is chlorinated with the addition of an average of 0.5-4-oh1orineatoms per molecule and the insecticidally active chlorination productproduced recovered.

7. Process according to claim 6, in which said chlorination is effectedwith the addition of about 2 chlorine.

atoms per molecule.

8. Process for the production of 4.5.6.7.10.l0-hexachloro-4.7endomethylene 4.7.8.9 tetrahydrophthalane which comprises heating amixture of dihydrofurane and hexachlorocyclopentadiene at a temperaturebetween about and C., and recovering from the reaction mixture thereaction product formed.

9. Process according to claim 8, in which said heat-ing is eflected inthe presence of a molar excess of one of the reactants.

10. Process according to claim 8, in which said heating is effected inthe presence of an inert diluent.

11. Process according to claim 8, in which saidhexachlorocyclopentadiene is present in a chlorinated reaction mixtureobtained from the reaction of cyclopentadione and an alkali hypochloritesolution.

12. Process according to claim 8, in which said recovered reactionproduct is chlorinated with the addition of an average of about 0.5-4atoms chlorine per molecule and the insecticidally active product formedrecovered.

13. Process according to claim 12, in which said chlorination iseffected with the addition of about 2 chlorine atoms per molecule.

14. The compound of the structural formula No references cited.

14. THE COMPOUND OF THE STRUCTURAL FORMULA